Olefin polymer and process for producing the same

ABSTRACT

An olefin polymer of an alkenyl hydrocarbon having 5 or more carbon atoms, wherein said olefin polymer is an amorphous polymer having a Mn of 300,000 and a Mw/Mn of 2.40 or less, and substantially not having a melting point, and a process for producing said olefin polymer which comprises polymerizing an alkenyl hydrocarbon having 5 or more carbon atoms with an olefin polymerization catalyst obtained by contacting: a specific transition metal compound(A), an organoaluminumoxy compound (B) soluble in an aromatic solvent and water (C).

This application is a divisional of application Ser. No. 09/237,798,filed on Jan. 27, 1999, now U.S. Pat. No. 6,232,421 the entire contentsof which are hereby incorporated by reference and for which priority isclaimed under 35 U.S.C. §120; and this application claims priority ofapplication Ser. No. 10-015757 filed in Japan on Jan. 28, 1998 under 35U.S.C. §119.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a specified amorphous polymer and aprocess for producing the same. More specifically, the present inventionrelates to an amorphous polymer having a high molecular weight enough toimprove problems such as stickiness, elution to an organic solvent andthe like, and to exhibit an elastomeric property and substantially nothaving a melting point and a process for producing said amorphouspolymer.

2. Description of Related Arts

An amorphous poly(α-olefin)(for example, an atactic polypropylene and anatactic poly(1-butene)) has been mainly used as a sticking agent, animproving agent for a crystalline polyolefin and the like. However, themolecular weight of an amorphous poly(α-olefin), as known well, is nothigh enough, therefore the amorphous poly(α-olefin) has problems such asstickiness of a product, elution to an organic solvent and the like, andit is difficult to say that an elastomeric property is sufficientlyexhibited.

With respect to a synthesis of the amorphous polymer, Some processeshave been known. It has been known from old times that a low-crystallinepolymer prepared as a by-product is recovered when an olefin ispolymerized with a solid Ziegler-Natta catalyst and an isotactic polymeris produced. However, the polymer obtained then has a low molecularweight and wide molecular weight distribution, and there have beenproblems such as stickiness of a product, elution to an organic solventand the like.

Further, there are a report (Chem. Commun., 1996, 783) in which a highmolecular weight poly(1-hexene)(Mn=1,252,000, Mw/Mn=2.70) can besynthesized by polymerizing 1-hexene under a ultra-high pressure of 250Mpa with a catalyst composed of using a hafnocene dichloride compoundand methyl aluminoxane, and a report (EP0604917 A2 and EP0604908 A2) inwhich a polypropylene having a weight average molecular weight Mw of377,000, a molecular weight distribution Mw/Mn(number average molecularweight) of 2.64 and a viscosity [η] of 2.28 dl/g, and a poly(1-butene)having a viscosity [η] of 1.29 dl/g, can be synthesized by polymerizingpropylene with a catalyst composed of dimethylsilylene bis(9-fluorenyl)zirconium dichloride and methyl alumoxane, but a polymer having anadequate high molecular weight and narrow molecular weight distributionis not obtained.

On the other hand, a polymer having a Mw of more than 8×10⁶ can besynthesized (Macromolecular Chemie, Rapid Communication, Vol.10 (1989),page 349) by polymerizing propylene using a transition metal compoundhaving an aryloxy ligand as a catalyst component, but the glasstransition temperature of the polymer was somewhat high and anelastomeric property was not sufficient. Further, in the polymerizationof an olefin having 5 or more carbon atoms with such catalyst, theresulted polymer was also not always satisfactory in the points ofstickiness and elution property to an organic solvent.

As described above, a poly(α-olefin of 5 or more carbon atoms) which hasan adequate high molecular weight and narrow molecular weightdistribution and no melting point substantially, and is amorphous, isnot obtained.

SUMMARY OF THE INVENTION

An object of the present invention is to provide an amorphous polymerhaving a high molecular weight enough to improve problems such asstickiness, elution to an organic solvent and the like, and to exhibitan elastomeric property, and substantially not having a melting point.

Another object of the present invention to provide a process forproducing said amorphous polymer.

Other objects and advantages of the present invention will be apparentfrom description below.

The present inventors have intensively studied to attain theabove-mentioned objects, and as a result, completed the presentinvention.

According to the present invention, there are provided an olefin polymerof an alkenyl hydrocarbon having 5 or more carbon atoms, wherein saidolefin polymer is an amorphous polymer having a polystyrene-reducednumber average molecular weight of 300,000 and a molecular weightdistribution of 2.40 or less in terms of a ratio of polystyrene-reducedweight average molecular weight (hereinafter, sometimes referred to as“Mw”) to polystyrene-reduced number average molecularweight(hereinafter, sometimes referred to as “Mn”) [Mw/Mn], andsubstantially not having a melting point, and a process for producingsaid olefin polymer which comprises polymerizing an alkenyl hydrocarbonhaving 5 or more carbon atoms with an olefin polymerization catalystobtained by contacting:

a transition metal compound (A) represented by the general formula (1)described below;

an organoaluminumoxy compound (B) soluble in an aromatic solvent; and

water (C), wherein the molar ratio of aluminum atom contained in theorganoaluminumoxy compound (B) to a transition metal atom contained inthe transition metal compound (A) is 1 to 20000, and the amount of waterused is 0.1 to 3.0 mol per 1 mol of aluminum atom contained in theorganoaluminumoxy compound (B).

(wherein M represents a transition metal atom of the Fourth Group of thePeriodic Table, X and Y independently represent a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a sulfonyloxy group, adi-substituted amino group or a substituted silyl group. R¹, R², R³, R⁴,R⁵, R⁶, R⁷ and R⁸ independently represent a hydrogen atom, an alkylgroup, an aryl group, an aralkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group. Further, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ maybe optionally bonded to form a ring. T represents a divalent covalentcrosslinking group having 1 to 20 carbon atoms, or a divalent grouprepresented by —O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—, —C(═O)—, —N(R⁹)—,—P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹ represents a hydrogen atom or ahydrocarbon group having 1 to 6 carbon atoms in each case), n is aninteger of from 0 to 3.).

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a flow chart to aid the understanding of the presentinvention. The flow chart is a representative example of the mode ofoperation of the present invention, and the present invention is notlimited thereto.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is explained in detail below.

An olefin polymer of the present invention is a polymer of an alkenylhydrocarbon having 5 or more carbon atoms and an amorphous polymerhaving a Mn of 300,000 or more and a Mw/Mn of 2.40 or less, andsubstantially not having melting point.

Specific examples of the alkenyl hydrocarbon having 5 or more carbonatoms, include an α-olefin having 5 or more carbon atoms such as1-pentene, 1-hexene, 3-methyl-1-pentene, 3-ethyl-1-penetene,4-methyl-1-penete, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and thelike, and vinylcyclohexane, and the like, and an alkenyl hydrocarbonhaving 5 to 20 carbon atoms is preferred. As the alkenyl hydrocarbonhaving 5 or more carbon atoms, a linear α-olefin is more preferable, and1-hexene or 1-octene is most preferable.

The olefin polymer of the present invention may be a copolymer. As acomonomer constituting the copolymer, a monomer copolymerizable with thealkenyl hydrocarbon having 5 or more carbon atoms, excluding 1-butene,can be used, and propylene or another alkenyl hydrocarbon having 5 ormore carbon atoms is preferable.

The content of the alkenyl hydrocarbon having 5 or more carbon atoms inthe polymer of the present invention is preferably 20 mol % or more,more preferably 50 mol % or more, and particularly preferable 70 mol %or more. Further, the most preferable olefin polymer of the presentinvention is a homopolymer of 1-hexene (poly(1-hexene)) or a homopolymerof 1-octene (poly(1-octene)).

The Mn of the olefin polymer of the present invention is 300,000 ormore, preferably 500,000 or more, and more preferably 800,000 or more.When the Mn of the olefin polymer is less than 300,000, it is notpreferable because problems such as stickiness and elution to an organicsolvent sometimes happen to occur.

Herein, the Mn described above and Mw described below mean apolystyrene-reduced number average molecular weight and apolystyrene-reduced weight average molecular weight, respectively,measured by gel permeation chromatography method.

The olefin polymer of the present invention has a Mw/Mn of 2.40 or less,preferably 2.3 or less, and more preferably 2.2 or less. When the Mw/Mnexceeds 2.40, it is not preferable because problems such as stickinessand elution to an organic solvent sometimes happen to occur.

The olefin polymer of the present invention is an amorphous polymersubstantially not having a melting point. The melting point is usuallymeasured with a differential scanning calorimeter (DSC) or the like. Inthe present invention, the term “substantially not having a meltingpoint” means that a crystal melting peak or crystallization peak is notsubstantially observed in the DSC measurement.

Such olefin polymer can be produced using, for example, said olefinpolymerization catalyst obtained by contacting a transition metalcompound (A) represented by the general formula (1) described above, anorganoaluminumoxy compound (B) soluble in an aromatic solvent, and water(C).

In the fore-mentioned general formula (1), M represents a transitionmetal atom of the Fourth Group of the Periodic Table (IUPAC InorganicChemistry Nomenclature, a revised edition, 1989) of elements, and atitanium atom, a zirconium atom or a hafnium atom is preferable and atitanium atom is more preferable.

In the general formula (1), respective X and Y independently represent ahydrogen atom, a halogen atom, an alkyl group, an aryl group, an aralkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, asulfonyloxy group, a di-substituted amino group or a substituted silylgroup.

Specific examples of such halogen atoms include a chlorine atom, abromine atom, an iodine atom and the like, and a chlorine atom ispreferable.

As the alkyl group in X or Y of the above-mentioned general formula (1),an alkyl group hydrocarbon having 1 to 24 carbon atoms is preferable.Specific examples thereof include methyl group, ethyl group, n-propylgroup, isopropyl group, n-butyl group, sec-butyl group, tert-butylgroup, n-pentyl group, neo-pentyl group, iso-pentyl group, 1-methylbutylgroup, n-hexyl group, n-octyl group, n-decyl group, n-dodecyl group,n-pentadecyl group, n-eicosyl group, and the like. Methyl group, ethylgroup, isopropyl group, tert-butyl group, n-pentyl group, neo-pentylgroup or iso-pentyl group is preferable.

Any one of these alkyl groups may be substituted with halogen atoms suchas a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxygroups such as methoxy group, ethoxy group and the like, and aryloxygroups such as phenoxy group and the like.

Examples of the alkyl group having 1 to 24 carbon atoms which issubstituted with a halogen atom include a fluoromethyl group, adifluoromethyl group, trifluoromethyl group, a chloromethyl group, adichloromethyl group, trichloromethyl group, a bromomethyl group, adibromomethyl group, tribromomethyl group, an iodomethyl group, adiiodomethyl group, triiodomethyl group, a fluoroethyl group, adifluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group,pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, atrichloroethyl group, a tetrachloroethyl group, pentachloroethyl group,a bromoethyl group, a dibromoethyl group, a tribromoethyl group, atetrabromoethyl group, a pentabromoethyl group, a perfluoropropyl group,a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group,a perfluorooctyl group, a perfluorododecyl group, a perfluoropentadecylgroup, a perfluoroeicosyl group, a perchloropropyl group, aperchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, aperchlorooctyl group, a perchlorododecyl group, a perchloropentadecylgroup, a perchloroeicosyl group, a perbromopropyl group, a perbromobutylgroup, a perbromopentyl group, a perbromohexyl group, a perbromooctylgroup, a perbromododecyl group, a perbromopentadecyl group, aperbromoeicosyl group, and the like. When various isomers exist, suchisomers are included.

Further, as the aryl group in X or Y in the general formula (1)described above, an aryl group having 6 to 24 carbon atoms ispreferable, and specific examples thereof include phenyl group, 2-tolylgroup, 3-tolyl group, 4-tolyl group, a 2,3-xylyl group, a 2,4-xylylgroup, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylylgroup, 2,3,4-trimethylphenyl group, 2,3,5-trimethylphenyl group,2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,3,4,5-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group,pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, aiso-propylphenyl group, a n-butylphenyl group, a sec-butylphenyl group,a tert-butylphenyl group, a n-pentylphenyl group, a neo-pentylphenylgroup, a n-hexylphenyl group, naphtyl group, an antharcenyl group, andthe like, and phenyl group is preferable. Any one of these aryl groupsmay be substituted with a halogen atom such as a fluorine atom, chlorineatom, bromine atom or an iodine atom, an alkoxy group such as methoxygroup, ethoxy group or the like, and an aryloxy group such as phenoxygroup or the like.

As the aralkyl group in X or Y in the general formula (1) describedabove, an aralkyl group having 7 to 24 carbon atoms is preferable, andspecific examples thereof include benzyl group, (2-methylphenyl)methylgroup, (3-methylphenyl)methyl group, (4-methylphenyl)methyl group,(2,3-dimethylphenyl)methyl group, (2,4-dimethylphenyl)methyl group,(2,5-dimethylphenyl)methyl group, (2,6-dimethylphenyl)methyl group,(3,4-dimethylphenyl)methyl group, (4,6-dimethylphenyl)methyl group,(2,4,6-trimethylphenyl)methyl group, (pentamethylphenyl)methyl group, a(ethylphenyl)methyl group, a (n-propylphenyl)methyl group, a(n-butylphenyl)methyl group, a (sec-butylphenyl)methyl group, a(tert-butylphenyl)methyl group, a (n-pentylphenyl) methyl group, a(neo-pentylphenyl)methyl group, naphtylmethyl group, antharcenylmethylgroup and the like, and benzyl group is preferable. Any one of thesearalkyl groups may be substituted with a halogen atom such as a fluorineatom, a chlorine atom, a bromine atom or an iodine, an alkoxy group suchas methoxy group, ethoxy group or the like, and an aryloxy group such asphenoxy group or the like.

As the alkoxy group in X or Y in the general formula (1) describedabove, an alkoxy group having 1 to 24 carbon atoms is preferable, andspecific examples thereof include methoxy group, ethoxy group, n-propoxygroup, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxygroup, n-pentoxy group, neopentoxy group, n-hexoxy group, n-octoxygroup, n-dodecoxy group, n-pentadecoxy group, n-icosoxy group, and thelike, and methoxy group, ethoxy group or tert-butoxy group ispreferable.

Any one of these alkoxy groups may be substituted with a halogen atomsuch as a fluorine atom, a chlorine atom, a bromine atom, or an iodineatom.

Further, as the aryloxy group in X or Y in the general formula (1)described above, an aryloxy group having 6 to 24 carbon atoms ispreferable and specific examples thereof include phenoxy group,2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group,2,3-dimethylphenoxy group, 2,4-dimethylphenoxy group,2,5-dimethylphenoxy group, 2,6-dimethylphenoxy group,3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group,2,3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group,2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group,2,4,6-trimethylphenoxy group, 3,4,5-trimethylphenoxy group,2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group,2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy group, anethylphenoxy group, a n-propylphenoxy group, an isopropylphenoxy group,a n-butylphenoxy group, a sec-butylphenoxy group, a tert-butylphenoxygroup, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxygroup, a n-tetradecylphenoxy group, a naphtoxy group, an antharcenoxygroup and the like. Phenoxy group is preferable. Any one of thesearyloxy groups may be substituted with a halogen atom such as a fluorineatom, chlorine atom, bromine atom or iodine atom.

As the aralkyloxy group in X or Y in the above-mentioned formula (1)described above, an aralkyloxy group having 7 to 24 carbon atoms ispreferable, and specific examples thereof include a benzyloxy group,(2-methylphenyl)methoxy group, (3-methylphenyl)methoxy group,(4-methylphenyl)methoxy group, (2,3-dimethylphenyl)methoxy group,(2,4-dimethylphenyl)methoxy group, (2,5-dimethyphenyl )methoxy group,(2,6-dimethylphenyl)methoxy group, (3,4-dimethylphenyl)methoxy group,(3,5-dimethylphenyl)methoxy group, (2,3,4-trimethylphenyl)methoxy group,(2,3,5-trimethylphenyl)methoxy group, (2,3,6-trimethylphenyl)methoxygroup, (2,4,5-trimethylphenyl)methoxy group,(2,4,6-trimethylphenyl)methoxy group, (3,4,5-trimethylphenyl)methoxygroup, (2,3,4,5-tetramethylphenyl)methoxy group,(2,3,5,6-tetramethylphenyl)methoxy group, (pentamethylphenyl)methoxygroup, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group,an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a(sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a(n-hexylphenyl)methoxy group, a (n-octylphenyl) methoxy group, a(n-decylphenyl)methoxy group, a n-tetradecylphenyl)methoxy group, anaphtylmethoxy group, an antharcenylmethoxy group and the like, and abenzyloxy group is preferable. Any one of these aralkyloxyl groups maybe substituted with halogen atoms such as a fluorine atom, a chlorineatom, a bromine atom or an iodine atom.

The sulfonyloxy group in X or Y in the general formula (1) describedabove represents a group indicated by the general formula R¹⁰SO₃— andrepresents a sulfonyloxy group having 1 to 24 carbon atoms which may beoptionally substituted. Specific examples thereof include those such asmethanesulfonyloxy group, ethanesulfonyloxy group, dodecylsulfonyloxygroup or the like whose R¹⁰ is an alkyl group, those such as atrifluoromethanesulfonyloxy group or the like whose a part issubstituted with a halogen atom, those such as p-toluenesulfonyloxygroup or the like whose R¹⁰ is an aryl group, or the like.

As the di-substituted amino group in X or Y in the general formula (1)described above, a di-substituted amino group having 2-24 carbon atomswhich is substituted with two hydrocarbon groups is preferable. Specificexamples the hydrocarbon groups include alkyl groups having 1 to 10carbon atoms such as methyl group, ethyl group, n-propyl group,isopropyl group, n-butyl group, sec-butyl group, tert-butyl group,isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group and thelike, aryl groups such as phenyl group and the like, etc. Examples ofsuch di-substituted amino group having 2 to 24 carbon atoms includedimethylamino group, diethylamino group, di-n-propylamino group,di-isopropylamino group, di-n-butylamino group, di-sec-butylamino group,di-tert-butylamino group, di-n-octylamino group, di-n-decylamino group,di-phenylamino group, bis-trimethylsilylamino group,bis-tert-butyldimethylsilylamino group and the like, and dimethylaminogroup or diethylamino group is preferable.

As the substituted silyl group in X or Y in the general formula (1)described above, a substituted silyl group having 1 to 24 carbon atoms,in other words, a silyl group substituted with a hydrocarbon group ispreferable. Examples of the hydrocarbon group include, for example,alkyl groups having 1 to 10 carbon atoms (e.g. methyl group, ethylgroup, n-propyl group, isopropyl group, n-butyl group, sec-butyl group,tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group,cyclohexyl group), aryl groups (e.g. phenyl group). Examples of suchsilyl group having 1 to 24 carbon atoms include a mono-substituted silylgroup having 1 to 20 carbon atoms such as methylsilyl group, ethylsilylgroup, phenylsilyl group or the like, a disubstituted silyl group having2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group,diphenylsilyl group or the like, a trisubstituted silyl group having 3to 20 carbon atoms such as trimethylsilyl group, triethylsilyl group,tri-n-propylsilyl group, tri-isopropylsilyl group, tri-n-butylsilylgroup, tri-sec-butylsilyl group, tri-tert-butylsilyl group,tri-isobutylsilyl group, tert-butyldimethylsilyl group,tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilylgroup, triphenylsilyl group and the like, and trimethylsilyl group,tert-butyldimethylsilyl group or triphenylsilyl group is preferable.

Any hydrocarbon group of these substituted silyl groups may besubstituted with a halogen atom such as a fluorine atom, chlorine atom,bromine atom or iodine atom.

These X and Y may optionally be bonded to form a ring. Each of a halogenatom, an alkyl group or an aralkyl group is independently preferable asX and Y in the fore-mentioned general formula (1), and chlorine atom,methyl group or benzyl group is more preferable.

Respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ in the fore-mentionedgeneral formula (1) independently represent a hydrogen atom, an alkylgroup, an aryl group, an aralkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group. Further, R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ mayoptionally be bonded to form a ring. Each of an alkyl group, an arylgroup, an aralkyl group, an alkoxy group, an aryloxy group, anaralkyloxy group, a di-substituted amino group or a substituted silylgroup in R¹, R², R³, R⁴, R⁵, R⁶, R⁷ or R⁸ is similar as in X or Y.

An aryl group or a substituted silyl group is preferable as R¹, R², R³,R⁴, R⁵, R⁶, R⁷ or R⁸ in the present invention.

In the fore-mentioned general formula (1), T represents a divalentcovalent cross-linking group having 1 to 20 carbon atoms, or a divalentgroup represented by —O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—, —C(═O)—,—N(R⁹)—, —P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹ represents a hydrogen atomor a hydrocarbon group having 1 to 6 carbon atoms in each case) and n isan integer selected from 0 to 3.)

As the divalent common cross-linking group having 1 to 20 carbon atoms,methylene group, ethylene group, trimethylene group, propylene group,diphenylethylene group, ethylidene group, propylidene group,isopropylidene group, n-butylidene group, isobutylidene group and thelike are exemplified. Among them, methylene group, ethylene group,ethylidene group, isopropylidene group, or isobutylidene group ispreferably used.

Further, in the divalent group represented by —N(R⁹)—, —P(R⁹)—, or—P(═O)(R⁹)— as T, R⁹ represents a hydrogen atom or a hydrocarbon grouphaving 1 to 24 carbon atoms in each case. As the hydrocarbon group, analkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24carbon atoms or an aralkyl group having 7 to 24 carbon atoms ispreferable. An alkyl group having 1 to 24 carbon atoms is morepreferable.

A divalent group represented by —O— or —S— is preferable as T, and —S—is more preferable.

n is an integer of 0 to 3, and represents the number of the unit T .Among these, 0 or 1 gives a preferable result in particular, and n ismore preferably 1.

The transition metal compound in the fore-mentioned general formula (1)can be easily produced and isolated. For example, the production process(I) and (II) described below are illustrated.

(I) A process for producing the transition compound by reacting acompound represented by the general formula (2) described below with atransition metal compound represented by the general formula (3)described below.

(II) A process for producing the transition compound by reacting acompound of the general formula (2) described below with anorganoalkaline metal compound, an alkaline metal hydride compound or anorganomagnesium compound (hereinafter, sometimes referred to as “themetal compound”) to obtain a halide compound and then reacting it withthe transition metal compound represented by the general formula (3)described below.

The halide compound may not be separated in the process (II). Further,it is also possible in the process (II) to mix together the compoundrepresented by the general formula (2), the metal compound and thetransition metal compound represented by the general formula (3) andreact them.

(Wherein respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ independentlyrepresent a hydrogen atom, an alkyl group, an aryl group, an aralkylgroup, an alkoxy group, an aryloxy group, an aralkyloxy group, adi-substituted amino group or a substituted silyl group, R¹, R², R³, R⁴,R⁵, R⁶, R⁷ and R⁸ may arbitrarily bond to form a ring, T represents adivalent covalent cross-linking group having 1 to 20 carbon atoms, or adivalent group represented by —O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—,—C(═O)—, —N(R⁹)—, —P(R⁹)—, or —P(═O)(R⁹)— (wherein R⁹ represents ahydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms in eachcase), and n is an integer of 0 to 3.)

MZ¹Z²Z³Z⁴  (3)

(wherein M represents a transition metal atom of the Fourth Group of thePeriodic Table, and respective Z¹, Z², Z³ and Z⁴ independently representa halogen atom, an alkoxy group, an aryloxy group, an aralkyloxy group,a di-substituted amino group, an alkyl group, an aryl group or anaralkyl group.)

Respective R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸ and T in the general formula(2) are the same as in the general formula (1).

As specific examples of the compound represented by the general formula(2), 2-(2-hydroxypropyl)phenol, cathecol, resorcinol,4-isopropylcathecol, 3-methoxycathecol, 1,8-dinydroxynaphthalene,1,2-dinydroxynaphthalene, 2,2′-biphenyldiol, 1,1′-bi-2-naphthol,2,2′-dihydroxy-6,6′-dimethylbiphenyl,4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenol,4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenol,2,2′-thiobis(4-methyl-6-isopropylphenol),2,2′-thiobis(4,6-dimethylphenol),2,2′-thiobis(4-methyl-6-tert-butyl)phenol and the like can beexemplified. Among these, 2,4-dihydroxypentane, cathecol,2,2′-biphenyldiol, 1,1′-bi-2-naphthol,4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenol,4,4′-dimethyl-6,6′-di-tert-butyl-2,2′-methylenediphenol,4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenol,2,2′-thiobis(4-methyl-6-isopropyl)phenol),2,2′-thiobis(4,6-dimethylphenol) and2,2′-thiobis(4-methyl-6-tert-butyl)phenol give a preferable result.

In the transition metal compound represented by the above-mentionedgeneral formula (3), Z¹, Z², Z³ and Z⁴ independently represent a halogenatom, an alkoxy group, an aryloxy group, an aralkyloxy group, asulfonyloxy group, a di-substituted amino group, an alkyl group, an arylgroup or an aralkyl group. Further, these may be optionally bonded inpart to form a ring.

Z¹, Z², Z³ and Z⁴ are the same as in X or Y in the above-mentionedgeneral formula (1). More specific examples of the transition metalcompound represented by the general formula (3) include titanium halidessuch as titanium tetrachloride, titanium tetrabromide, titaniumtetraiodide and the like, titanium amides such astetrakis(dimethylamino) titanium, dichlorobis(dimethylamino) titanium,trichloro(dimethylamino) titanium, tetrakis(diethylamino) titanium andthe like, alkoxytitaniums such as tetraisopropoxytitanium, tetran-butoxytitanium, diisopropoxytitanium dichloride, isopropoxytitaniumtrichloride and the like, and compounds in which titanium in theabove-mentioned compounds is replaced with zirconium or hafnium, etc.

In the production process (I) or (II), the amount used of the transitionmetal compound represented by the general formula (3) is usually 0.5 to3-fold mol, and preferably 0.7 to 1.5-fold mol based on the compoundrepresented by the general formula (2).

Specific examples of the organoalkaline metal compound used in theproduction process (II) include organolithium compounds such asmethyllithium, ethyllithium, n-butyllithium, sec-butyllithium,tert-butyllithium, lithium trimethylenesilyl acetylide, lithiumacetylide, trimethylsilyl methyllithium, vinyllithium, phenyllithium,allyllithium and the like, organoalkaline metal compounds in whichlithium in these compounds is replaced with sodium, potassium, rubidiumor cesium. Preferably, an alkaline metal compound having an alkyl groupwith 1 to 10 carbon atoms is preferred, a compound having an alkyl groupwith 1 to 10 carbon atoms of lithium, sodium or potassium is morepreferred, and an alkyllithium compound having an alkyl group with 1 to10 carbon is most preferred.

The alkaline metal hydride is a hydride of lithium, sodium, potassium,rubidium or cesium, and sodium hydride or potassium hydride ispreferred.

Examples of the organomagnesium compound include dialkylmagnesiumcompounds and alkylmagnesium halides, and specifically,dimethylmagnesium, diethylmagnesium, di-n-butylmagnesium,diisopropylmagnesium, n-butylethylmagnesium, methylmagnesium iodide,methylmagnesium chloride, isopropylmagnesium halide and the like.Alkylmagnesium halides having an alkyl group of 1 to 10 carbon atoms arepreferred.

As the above-mentioned metal compounds, organoalkaline metal compoundsor alkaline metal hydrides are preferable and the alkyllithium is morepreferable. The amount used of the metal compound in the productionprocess (II) is usually 1 to 5-fold mol based on the compoundrepresented by the general formula (2).

The reaction is generally carried out in the presence of a solvent.Examples of the solvent used include an aprotic solvent of an aromatichydrocarbon such as benzene, toluene, xylene, mesitylene or the like, analiphatic hydrocarbon such as pentane, hexane, heptane, octane or thelike, an ether type solvent such as diethyl ether, tetrahydrofuran,1,4-dioxane or the like, an amide type solvent such ashexamethylphosphoric amide, dimethyl amide, a polar solvent such asacetonitrile, propionitrile, acetone, diethyl ketone, methylisobutylketone, cyclohexanone or the like, a halogenated solvent such asdichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, or thelike, etc. Such solvent is used alone or two or more in combination, andthe amount used thereof is usually 1 to 200 ml/g based on the volume toweight of the compound represented by the general formula (2) andPreferably 3 to 50 ml/g.

The reaction (I) can be carried out in the presence of a tertiaryaminecompound or the like, and triethylamine and diisopropylethylamine,N,N,N′,N′-tetramethylethylenediamine and the like are preferably used asthe tertiaryamine compound as an additive aid. The amount used is 1 to10-fold mol based a compound represented by the general formula (2),preferably 1.5 to 5-fold mol and more preferably 1.8 to 4-fold mol.

The reaction of the production process (I) is carried out in a range of−100° C. to 200° C., and preferably −80° C. to 150° C. A range of −50°C. to 120° C. is more preferable. The reaction temperature in theproduction process (II) is usually from −100° C. to the boiling point ofthe solvent used as a medium, but when the organoalkaline metal is used,a range of −80° C. to 40° C. is preferable and when the organomagnesiumcompound is used, a range of 10° C. to 100° C. is preferable,respectively.

When there is a solid component which is produced as a by-product by thereaction from the reaction mixture containing the transition metalcompound represented by the general formula (I) according to theabove-mentioned reaction, it is separated by filtration or the like inthe presence of a predetermined solvent, and further, after heating andconcentrating the solvent or by standing alone in another solvent aloneor a mixed solvent at a cooled dark place, crystals of the complex canbe separated. Further, it is possible to efficiently precipitate thedesired complex in high purity to take out, while industrially stirringwithout standing alone, for example, cooling gradually.

The compound represented by the general formula (2) in the presentinvention is produced by various processes. For example, when T is asulfur atom, the compound can be easily synthesized by reacting variouskind of phenol compounds with sulfur dichloride in a solvent whilestirring.

The solvent used includes an aprotic solvent of an aliphatic hydrocarbonsuch as pentane, hexane, heptane, octane or the like, an etheral solventsuch as diethyl ether, tetrahydrofuran, 1,4-dioxane or the like, ahalogenated hydrocarbon solvent such as dichloromethane, dichloroethane,chlorobenzene, dichlorobenzene or the like, etc.

The component (B) in the above-mentioned olefin polymerization catalystis an organoaluminumoxy compound soluble in an aromatic hydrocarbonsolvent. The examples thereof include methylaluminoxane,ethylaluminoxane, propylaluminoxane, butylaluminoxane,isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane,methylisobutylaluminoxane, the organoaluminumoxy compound represented bythe general formula (4) or (5) described below, and the like. Amongthem, methylisobutylaluminoxane, and the organoaluminumoxy compoundsrepresented by the general formula (4) and (5) described below arepreferred.

(wherein R represents methyl group or isobutyl group, the presence ratioof a methyl group and an isobutyl group is methyl group: isobutylgroup=5 to 95:95 to 5. m represents a number in a range of 1 to 50.)

The organoaluminumoxy compound soluble in an aromatic hydrocarbonsolvent which is used in the present invention can form a componentinsoluble in the aromatic hydrocarbon solvent by reacting with water.

The amount of the organoaluminumoxy compound used can be usuallyselected in a wide range of 1 to 20,000 mol in terms of an aluminum atomcontained in the organoaluminumoxy compound per one mol of a transitionmetal atom contained in the transition metal compound (A). Thepreferable range is from 100 to 10,000 mol per one mol of the transitionmetal atom.

Water is used as the component (C) in the above-mentioned olefinpolymerization catalyst. The amount of the water (C) used can be usuallyselected in a wide range of 0.1 to 3.0 mol per one mol of an aluminumatom contained in the organoaluminumoxy compound (B). The preferablerange is from 0.1 to 1.0 per one mol of the aluminum atom.

As a method of feeding the respective catalyst components in apolymerization reactor, a transition metal compound (A), an aromaticorganoaluminumoxy compound (B) and water (C) may be separately fed ormay be fed after contacting them in advance.

Specific examples of a method of previously contacting include a methodof contacting an organoaluminumoxy compound (B) with water (C) and thenremoving the solvent followed by contacting with the component (A), amethod of contacting the component (B) with the component (C) and thencontacting with the component (A), a method of contacting the component(A), the component (B) and the component (C) at the same time, and thelike. Examples of a contacting method of the component (C) include amethod of directly contacting water, a method of previously mixing waterwith a solvent and contacting the mixture with other components, amethod of contacting a metal salt containing a crystal water or aninorganic or organic material containing absorbed water with othercomponents, a method of contacting a gas such as nitrogen containingmoisture, or the like with other components, etc. when the component (B)is contacted with the component (C), a component insoluble in anaromatic hydrocarbon solvent sometimes form.

Polymerization is usually carried out over a wide range of −30 to 300°C., preferably 0 to 280° C. and more preferably 20 to 250° C.

The polymerization pressure is not particularly restricted, and ispreferably from about normal pressure to about 150 atom from industrialand economic viewpoints. The polymerization time is suitably determinedaccording to a kind of the desired polymer and a reaction apparatus ingeneral, and adopts a range of 30 seconds to 40 hours.

As a polymerization process, either of batch type and continuous typeare applicable. Further, a slurry or solution polymerization with aninert hydrocarbon solvent such as propane, pentane, hexane, heptane,octane or the like, a bulk polymerization using a monomer as a solventor a gas phase polymerization is applicable.

A chain transfer agent such as hydrogen or the like can be added inorder to control the molecular weight of the olefin polymer.

EXAMPLE

The present invention is specifically illustrated according to Examplesbelow, but the scope of the present invention is not restricted byExamples.

The value of respective items in Examples was measured by methodsdescribed below.

(1) Polystyrene-Reduced Weight Average Molecular Weight (Mw),Polystyrene-Reduced Number Average Molecular Weight (Mn) and MolecularWeight Distribution (Mw/Mn)

They were measured with a gel permeation chromatograph (GPC) underconditions described below. A calibration curve was prepared using astandard polystyrene.

Measuring instrument: 150 CV type manufactured by Millipore WatersCompany Ltd.

Column: Shodex M/S 80

Measurement temperature: 145° C.,

Solvent: Ortho-dichlorobenzene

Sample concentration: 5 mg/8 ml

(2) Measurement with a Differential Scanning Calorimeter (DSC)

It was measured under the conditions below using DSC-VII manufactured byPerkin-Elmer Company, Ltd.

Raising temperature: 20° C. to 200° C. (20° C/min.), retention for 10min.

Cooling: 200° C. to −100° C. (20° C/min.), retention for 10 min.

Measurement: −100° C. to 300° C. (raising temperature at 20° C./min.)

Reference Example 1

Synthesis of Dichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato]}titanium

The title compound was synthesized according to a literature (Arjan vander Linden et. al., Journal of the American Chemical Society, 117,3008(1995))

Example 1

An egg-plant type flask with an inner volume of 300 ml was replaced withargon, 20 mmol of (poly)methylisobutyl aluminoxane (hereinafter,sometimes abbreviated to as “MMAO”) manufactured by Tosoh-Akzo Co., Ltd.of toluene solution and 11 mmol of water were added therein and themixture was mixed by stirring for 10 minutes.

On the other hand, in an egg-plant type flask with an inner volume of 25ml replaced with argon, 5 ml of purified toluene and 1.2 mg ofdichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask. The molar ratio of [Al]/[Ti] of the catalyst solutionprepared then was 8,000. After the catalyst solution was mixed bystirring at room temperature for 10 minutes, 63 ml of 1-hexene wascharged and the polymerization was carried out at 40° C. for 3 minutes.After completion of the polymerization, the contents in the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.63 g of poly(1-hexene) copolymer was obtained. Mw of thepolymer obtained was 566×10⁴, Mn was 297×10⁴, Mw/Mn was 1.9, no crystalfusion peak by DSC was detected, and the polymer was amorphous. Theglass transition temperature was observed at −46° C.

Example 2

An egg-plant type flask with an inner volume of 100 ml was replaced withargon, 20 mmol of MMAO and 11 mmol of water were added therein and themixture was mixed by stirring for 10 minutes.

On the other hand, in an egg-plant type flask with an inner volume of 25ml replaced with argon, 5 ml of purified toluene and 1.2 mg ofdichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask of 100 ml. The molar ratio of [Al]/[Ti] of the catalystsolution prepared then was 8,000. After the catalyst solution was mixedby stirring at room temperature for 10 minutes, 31.2 ml of 1-octene wascharged and the polymerization was carried out at 40° C. for 10 minutes.After completion of the polymerization, the contents of the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.12 g of poly(1-octene) copolymer was obtained. Mw of thepolymer obtained was 599×10⁴, Mn was 294×10⁴, Mw/Mn was 2.0, no crystalfusion peak by DSC was detected, and the polymer was amorphous. Theglass transition temperature was observed at −61° C.

Comparative Example 1

An egg-plant type flask with an inner volume of 50 ml was replaced withargon, and 1 mmol of MMAO was added therein.

On the other hand, in an egg-plant type flask with an inner volume of 25ml replaced with argon, 2 ml of purified toluene and 4.8 mg ofdichloro{2,2′-thiobis[4-methyl-6-(tert-butyl)phenolato} titanium weremixed by stirring, and then charged into the above-mentioned egg-planttype flask of 50 ml. The molar ratio of [Al]/[Ti] of the catalystsolution prepared then was 100. After the catalyst solution was mixed bystirring at room temperature for 10 minutes, 6.3 ml of 1-hexene wascharged and the polymerization was carried out at 40° C. for 1 hour.After completion of the polymerization, the contents of the flask werecharged into about 400 ml of an acidic methanol, and the precipitatedpolymer was filtered to be dried at 80° C. for about 2 hours. As aresult, 0.31 g of poly(1-hexene) was obtained. Mw of poly(1-hexene)obtained was 20×10⁴ Mn was 8×10⁴, Mw/Mn was 2.5.

As described above, according to the present invention, an amorphouspolymer having a high molecular weight enough to improve problems suchas stickiness and elution to an organic solvent and to exhibit anelastomeric property, and substantially not having a melting point, anda process for producing the amorphous polymer, are provided.

What is claimed is:
 1. A process for producing an olefin polymer of analkenyl hydrocarbon having 5 or more carbon atoms, wherein said olefinpolymer has a polystyrene-reduced number average molecular weight of300,000 or more, and a molecular weight distribution of 2.40 or less interms of ratio of polystyrene-reduced weight average molecular weight topolystyrene-reduced number average molecular weight, and is an amorphouspolymer substantially not having a melting point, comprising:polymerizing an alkenyl hydrocarbon having 5 or more carbon atoms withan olefin polymerization catalyst obtained by contacting: a transitionmetal compound (A) represented by the formula (1) described below;

wherein, M represents a transition metal atom of the Fourth Group of thePeriodic Table; X and Y independently represent a hydrogen atom, ahalogen atom, an alkyl group, an aryl group, an aralkyl group, an alkoxygroup, an aryloxy group, an aralkyloxy group, a sulfonyloxy group, adi-substituted amino group or a substituted silyl group; R¹, R², R³, R⁴,R⁵, R⁶, R⁷ and R⁸ independently represent a hydrogen atom, an alkylgroup, an aryl group, an aralkyl group, an alkoxy group, an aryloxygroup, an aralkyloxy group, a di-substituted amino group or asubstituted silyl group; R², R³, R⁴, R⁵, R⁶, R⁷ and R⁸ may be optionallybonded to form a ring; T represents a divalent covalent crosslinkinggroup having 1 to 20 carbon atoms, or a divalent group represented by—O—, —S—, —S—S—, —S(═O)—, —S(═O)₂—, —C(═O)—, —N(R⁹)—, —P(R⁹)— or —P(═O)(R⁹)—, wherein R⁹ represents a hydrogen atom or a hydrocarbon grouphaving 1 to 6 carbon atoms; and n is an integer of from 0 to 3; anorganoaluminumoxy compound (B) soluble in an aromatic solvent; and water(C), wherein the molar ratio of aluminum atom contained in theorganoaluminumoxy compound (B) to a transition metal atom contained inthe transition metal compound (A) is 1 to 20000, and the amount of waterused is 0.1 to 3.0 mol per aluminum atom contained in theorganoaluminumoxy compound (B).
 2. The process according to claim 1,wherein T is a divalent group represented by —S—.
 3. The processaccording to claim 1, wherein the organoaluminumoxy compound (B) solublein an aromatic solvent is methylisobutylalumoxane.
 4. The processaccording to claim 1, wherein the organoaluminumoxy compound (B) solublein an aromtaic hydrocarbon solvent is an organoaluminumoxy compoundrepresented by formula (4) or (5):

wherein R represents methyl group or isobutyl group, the presence ratioof methyl group and isobutyl group is methyl group: isobutyl group=5 to95:95 to 5; Al represents aluminum atom; and m represents a number of 1to
 5. 5. The process according to claim 1, wherein the amount oforganoaluminumoxy (B) is 100 to 20,000 mol in terms of aluminum atomcontained in the organoaluminumoxy compound per one mol of thetransition metal atom contained the the transition metal compound (A),and the amount of the water (C) is 0.1 to 1.0 mol per one mol of analuminum atom contained in the organoaluminumoxy compound (B).
 6. Theprocess according to claim 1, wherein the alkenyl hydrocarbon having 5or more carbon atoms is 1-hexene or 1-octene.